KR101340864B1

KR101340864B1 - Active carbon-transition metal oxide for electrode active material and manufacturing method of the same

Info

Publication number: KR101340864B1
Application number: KR1020120031543A
Authority: KR
Inventors: 노광철; 김목화; 박선민; 한상진; 우대중
Original assignee: 비나텍주식회사; 한국세라믹기술원
Priority date: 2012-03-28
Filing date: 2012-03-28
Publication date: 2013-12-12
Also published as: KR20130116455A

Abstract

The present invention relates to an anode or cathode electrode as a nanocomposite material in which a transition metal oxide is composited into porous activated carbon having a plurality of pores having an average interlayer distance d ₀₀₂ in a range of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged. Used as an active material, the transition metal oxide is M (O) _{n / 2} , where M is an n-valent transition metal, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Cd, Zn, Ru, The present invention relates to an activated carbon-transition metal oxide composite electrode active material and a method of manufacturing the same, wherein the material has a chemical formula of Pd, Ag, Pt, and Au. According to the present invention, a nanocomposite material having a transition metal oxide complexed to a porous activated carbon having a plurality of pores having an average interlayer distance d ₀₀₂ in the range of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged is obtained. By using it as an electrode active material, it is possible to manufacture a supercapacitor electrode having a high specific capacitance and an energy density.

Description

Active carbon-transition metal oxide for electrode active material and manufacturing method of the same}

The present invention relates to an electrode active material and a method of manufacturing the same, and more particularly, a transition metal to a porous activated carbon having a plurality of pores having an average interlayer distance d ₀₀₂ in the range of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged. The present invention relates to an activated carbon-transition metal oxide composite electrode active material capable of having a high specific capacitance and an energy density by using an oxide-composite nanocomposite material as an electrode active material of a cathode or an anode, and a method of manufacturing the same.

Supercapacitors are also commonly referred to as Electric Double Layer Capacitors (EDLCs), Supercapacitors or Ultracapacitors, which are the interface between electrodes and conductors and the electrolyte solution impregnated therewith. By using a pair of charge layers (electric double layers) each having a different sign, the deterioration due to repetition of the charge / discharge operation is very small and requires no maintenance. As a result, supercapacitors are widely used in IC (integrated circuit) backup of various electric and electronic devices. Recently, they have been widely used for toys, solar energy storage, HEV (hybrid electric vehicle) have.

Such a supercapacitor generally includes two electrodes of a positive electrode and a negative electrode impregnated with an electrolytic solution, a separator of a porous material interposed between the two electrodes to enable ion conduction only and to prevent insulation and short circuit, A gasket for preventing leakage of electricity and preventing insulation and short-circuit, and a metal cap as a conductor for packaging them. Then, one or more unit cells (normally 2 to 6 in the case of the coin type) are stacked in series and the two terminals of the positive and negative electrodes are combined.

The performance of the supercapacitor is determined by the electrode active material and the electrolyte. In particular, the main performance such as the capacitance is largely determined by the electrode active material. Activated carbon is mainly used as the electrode active material, and the specific storage capacity is known to be about 19.3 F / cc as the electrode standard of commercial products. In general, activated carbon used as an electrode active material of a supercapacitor has a high specific surface area activated carbon of 1500 m 2 / g or more.

However, with the expansion of applications of supercapacitors, higher specific capacitances and energy densities are required, and thus, development of activated carbons expressing higher capacitances is required.

A supercapacitor using activated carbon powder as an electrode is disclosed in Japanese Patent Laid-Open No. 4-44407. The electrode proposed in this publication is a solid activated carbon electrode obtained by solidifying a mixture of activated carbon powder with a thermosetting resin such as a phenol resin.

Japanese Patent Laid-Open No. 4-44407

The problem to be solved by the present invention is a positive electrode or a nanocomposite composite of a transition metal oxide composite to a porous activated carbon having a plurality of pores having an average interlayer distance d ₀₀₂ is 3.602 ~ 4.445 공 and provides a passage through which electrolyte ions are introduced or discharged The present invention provides an activated carbon-transition metal oxide composite electrode active material and a method of manufacturing the same, which can have high specific capacitance and energy density by using as an electrode active material of a negative electrode.

The present invention relates to an anode or cathode electrode as a nanocomposite material in which a transition metal oxide is composited into porous activated carbon having a plurality of pores having an average interlayer distance d ₀₀₂ in a range of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged. Used as an active material, the transition metal oxide is M (O) _{n / 2} , where M is an n-valent transition metal, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Cd, Zn, Ru, Provided is an activated carbon-transition metal oxide composite electrode active material, characterized in that the material having a chemical formula of one or more transition metals selected from Pd, Ag, Pt and Au.

The specific surface area of the porous activated carbon is preferably in the range of 300 to 1300 m 2 / g.

In addition, the present invention provides a method for preparing a porous activated carbon powder having a plurality of pores having an average interlayer distance d ₀₀₂ in the range of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged, and complexing with a transition metal oxide. To facilitate the oxidation of the porous activated carbon powder in an acidic solution, and adding and mixing the acidic solution containing the oxidized porous activated carbon powder to the aqueous solution of the transition metal oxide precursor serving as a source of the transition metal And obtaining a precipitate by titrating an alkali compound in the transition metal oxide precursor aqueous solution mixed with the porous activated carbon powder, and selectively separating the precipitate to obtain a material in which the transition metal hydroxide is complexed with the porous activated carbon. Oxidizing atmosphere of transition metal hydroxide complex Standing the heat treatment by the activated carbon-transition activated carbon comprising the steps of obtaining a composite metal oxide electrode active material transitions provide a method for producing metal oxide composite electrode active material.

The heat treatment is preferably carried out in an oxidizing atmosphere at a temperature of 200 ~ 600 ℃.

The acidic solution may be composed of at least one acid solution selected from hydrochloric acid (HCl), nitric acid (HNO ₃ ) and sulfuric acid (H ₂ SO ₄ ), and the acidic solution has a molar concentration of 0.1 for sufficient oxidation treatment. It is preferable that it is a range of -5M.

The transition metal oxide precursors are M (NO ₃ ) _n , M (CO ₃ ) _{n / 2} , M (SO ₄ ) _{n / 2} , MCl _n (M is an n-valent transition metal, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Cd, Zn, Ru, Pd, Ag, Pt and Au may be composed of nitrate, carbonate, sulfate or chloride represented by one or more transition metals), the transition metal oxide precursor It is preferable that the aqueous solution has a molar concentration in the range of 0.1 to 5 M.

The alkali compound may be at least one material selected from lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), and ammonia water (NH ₄ OH), wherein the alkali compound has a molar concentration in the range of 0.1 to 10M. It is preferable.

It is preferable to titrate the said alkali compound so that pH may be 8-12.

The preparing of the porous activated carbon powder may include carbonizing the carbon material in an inert atmosphere at a temperature in the range of 550 to 1000 ° C., activating the carbonized carbon material with alkali, and activating the resultant. Neutralizing with acid and washing.

The activating treatment may include mixing the carbonized carbon material and the alkali in a weight ratio of 1: 1 to 1: 5, pulverizing the mixed product and in an inert atmosphere at a temperature of 600 to 900 ° C. It may include the step of heat treatment, the alkali may be potassium hydroxide (KOH) or potassium hydroxide (NaOH).

It is preferable that the specific surface area of the said porous activated carbon powder is 300-1300 m <2> / g.

In addition, the present invention provides a method for preparing a porous activated carbon powder having a plurality of pores having an average interlayer distance d ₀₀₂ in the range of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged, and complexing with a transition metal oxide. Oxidizing the porous activated carbon powder in an acidic solution for ease of treatment, selectively separating the oxidized porous activated carbon, washing and drying, and dispersing the dried porous activated carbon in distilled water; Adding and mixing an aqueous solution of a transition metal oxide precursor serving as a source of transition metal to a dispersion containing porous activated carbon, and titrating an alkali compound in a solution containing the aqueous dispersion and transition metal oxide precursor solution containing the porous activated carbon. Step, and the mixed solution formed by titrating the alkali compound The activated carbon-transition metal oxide composite electrode active material comprising charging to an oven and heat treatment using a microwave, and washing and drying the reaction product formed by heat treatment to obtain a nanocomposite composite of a transition metal oxide in a porous activated carbon. It provides a manufacturing method.

Heat treatment using the microwave is preferably carried out in an oxidizing atmosphere at a temperature of 100 ~ 200 ℃.

It is preferable to titrate the said alkali compound so that pH may be 8-12.

According to the present invention, an active carbon-transition metal oxide composite electrode active material having a plurality of pores having an average interlayer distance d ₀₀₂ in a range of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged is used as an electrode active material of a cathode or an anode. As a result, a supercapacitor electrode having a high specific capacitance and an energy density can be obtained.

1 is a view schematically showing a coin-type supercapacitor as a state diagram of use of the activated carbon-transition metal oxide composite electrode active material according to the present invention.
2 is a view illustrating a state in which lead wires are attached to a positive electrode and a negative electrode.
3 is a view showing a state in which a book revoker is formed.
4 is a view showing a state in which the bookbinding canceller is inserted into the metal cap.
5 is a diagram illustrating a part of the supercapacitor cut away.
6 is a high resolution-transmission electron microscope (HR-TEM) photograph of an activated carbon-transition metal oxide composite electrode active material prepared according to Experimental Example 1. FIG.
7 is a graph showing an X-ray diffraction (XRD) pattern of the activated carbon-transition metal oxide composite electrode active material prepared according to Experimental Example 1. FIG.
8 is a schematic view of a three-electrode cell.
9 is a plan view of the three-electrode cell viewed from above.
FIG. 10 is a cycle measuring the current value of an electrode when the electrode potential of the three-electrode cell shown in FIGS. 8 and 9 is changed while maintaining a constant scan rate at a constant potential scanning rate within a potential window. A cyclic voltammogram graph.
FIG. 11 shows the charge and discharge test results of the supercapacitor manufactured according to Experimental Example 1. FIG.
12 is a charge and discharge test graph of the supercapacitor prepared according to Experimental Example 3.
13 is a graph showing specific capacitance according to precursor carbonization temperature of a supercapacitor manufactured according to Experimental Example 3. FIG.
14 is a graph showing the average interlayer distance according to the carbonization temperature of the supercapacitor manufactured according to Experimental Example 3.
FIG. 15 is a high-resolution electron microscope (HR-TEM) photograph showing a carbon material before carbonization treatment after carbonization according to Experimental Example 3. FIG.
FIG. 16 is a high-resolution electron microscope (HR-TEM) photograph showing porous activated carbon prepared according to Experimental Example 3. FIG.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not. Wherein like reference numerals refer to like elements throughout.

In the following description, 'nano' is used to mean a size in the range of 1 nm to 1000 nm as the size in nanometers (nm), and 'nano composite material' is 1 nm as the size in nanometers (nm) It is used to mean a composite having a particle size in the range from 1000nm.

The activated carbon-transition metal oxide composite electrode active material according to a preferred embodiment of the present invention is a transition to porous activated carbon having an average interlayer distance d ₀₀₂ of 3.602 to 4.445 kPa and having a plurality of pores that provide passages through which electrolyte ions are introduced or discharged. A nanocomposite material in which a metal oxide is complexed is used as an electrode active material of a positive electrode or a negative electrode, and the transition metal oxide is M (O) _{n / 2} (where M is an n-valent transition metal, and Ti, V, Cr, Mn, And Fe, Co, Ni, Cu, Cd, Zn, Ru, Pd, Ag, Pt and Au.

The specific surface area of the porous activated carbon may range from 300 to 1300 m 2 / g.

In a method of manufacturing a supercapacitor electrode according to an exemplary embodiment of the present invention, a porous activated carbon powder having a plurality of pores having an average interlayer distance d ₀₀₂ of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged is prepared. And oxidizing the porous activated carbon powder in an acidic solution to facilitate complexation with the transition metal oxide, and using the acidic solution including the oxidized porous activated carbon powder as a source of transition metal. Adding to the aqueous transition metal oxide precursor solution and mixing; obtaining a precipitate by titrating an alkali compound to the aqueous transition metal oxide precursor solution in which the porous activated carbon powder is mixed; and selectively separating the precipitate to form a transition metal in the porous activated carbon Obtaining a composite material of hydroxide and porous activity Annealing the transition metal hydroxide is a composite material in an oxidizing atmosphere, and a step for obtaining the transition metal oxide, a composite nano-composite material on a porous activated carbon.

It is preferable to titrate the said alkali compound so that pH may be 8-12.

According to another preferred embodiment of the present invention, a method of manufacturing a supercapacitor electrode includes preparing a porous activated carbon powder having a plurality of pores having an average interlayer distance d ₀₀₂ of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged. And oxidizing the porous activated carbon powder in an acidic solution to facilitate complexation with the transition metal oxide, and selectively separating the oxidized porous activated carbon, followed by washing and drying, and drying Dispersing the porous activated carbon in distilled water, adding and mixing an aqueous solution of a transition metal oxide precursor serving as a source of transition metal to a dispersion containing porous activated carbon, and a dispersion and a transition metal oxide precursor containing the porous activated carbon Titrating an alkali compound to a solution mixed with an aqueous solution, and Charging the mixed solution formed by titration of the kali compound into a microwave oven and heat-treating with microwave, and washing and drying the reaction product formed by heat treatment to obtain a nanocomposite material having a transition metal oxide mixed with porous activated carbon. Include.

It is preferable to titrate the said alkali compound so that pH may be 8-12.

The porous activated carbon powder used in the present invention is composed of porous carbon having an average interlayer distance d ₀₀₂ of 3.602 to 4.445 kPa and a specific surface area of 300 to 1300 m 2 / g. The porous activated carbon is a porous material having numerous pores that provide passages through which electrolyte ions, dispersion media, and the like are introduced or discharged.

The porous activated carbon may be obtained by carbonizing and activating a graphitizable carbon material. The graphitizable carbon material may be pitch or coke or the like.

Hereinafter, a method of preparing the porous activated carbon powder will be described in more detail.

A graphitizable carbon material is prepared, and the graphitizable carbon material is carbonized. Graphitizable carbon materials may be petroleum pitch, coal based pitch, petroleum coke, coal based coke and the like. The carbonization treatment is preferably carried out in an inert atmosphere for 10 minutes to 12 hours at a temperature of about 550 to 1000 ℃, preferably about 700 to 750 ℃. The inert atmosphere refers to a gas atmosphere such as nitrogen (N ₂ ) and arcon (Ar).

The activation treatment is performed on the carbonized carbon material. In the activation treatment, carbonized carbon material and alkali such as potassium hydroxide (KOH), potassium hydroxide (NaOH), etc. are mixed and pulverized in a ratio of 1: 1 to 1: 5 in a weight ratio, and then the temperature is about 600 to 900 ° C. It is preferably carried out in an inert atmosphere for 10 minutes to 12 hours.

The milling may be performed by ball milling, jet milling or the like. As a specific example of the grinding step, the ball milling step will be described. The graphitizing carbon material is charged into a ball milling machine, and is milled by rotating at a constant speed using the ball milling machine. The size of the balls, the milling time, the rotation speed of the ball miller, and the like are adjusted so as to be crushed to the target particle size. As the milling time increases, the particle size of the graphitized carbon powder gradually decreases, thereby increasing the specific surface area. The balls used for ball milling can be ceramic balls such as alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), and the balls may be all the same size or may be used together with balls having two or more sizes It is possible. The size of the ball, the milling time, and the rotation speed per minute of the ball mill are adjusted. For example, the size of the ball is set in the range of about 1 to 30 mm, and the rotation speed of the ball mill is about 50 to 500 rpm And ball milling can be performed for 1 to 50 hours.

After the activation treatment, neutralization treatment with an acid such as hydrochloric acid (HCl) and nitric acid (HNO ₃ ) in order to remove the alkaline component, followed by rinsing with distilled water is sufficient. After washing, it is sufficiently dried for 10 minutes to 6 hours at a temperature of about 100 to 180 ° C.

In the above-described process, it is possible to obtain porous activated carbon powder having an average interlayer distance d ₀₀₂ of 3.602 to 4.445 kPa and a specific surface area of 300 to 1300 m 2 / g and having a plurality of pores. When used as a supercapacitor electrode, the pores formed in the porous activated carbon powder serve to provide a passage through which electrolyte ions are introduced or discharged.

The activated activated carbon-transition metal oxide composite electrode active material is formed by complexing the porous activated carbon powder and the transition metal oxide thus prepared. Hereinafter, embodiments of the method of manufacturing the activated carbon-transition metal oxide composite electrode active material will be described in more detail.

&Lt; Example 1 >

Porous activated carbon powder is oxidized in an acid solution. The oxidation treatment is intended to facilitate complexation with the transition metal oxide by improving the porous activated carbon powder. The acidic solution is preferably made of at least one acid solution selected from hydrochloric acid (HCl), nitric acid (HNO ₃ ) and sulfuric acid (H ₂ SO ₄ ). In addition, the acidic solution is preferably a molar concentration of about 0.1 to 5M for sufficient oxidation treatment.

The acidic solution containing the oxidized porous activated carbon powder is added to the aqueous transition metal oxide precursor solution and mixed. Transition metal oxide precursors are nitrates, carbonates, sulfates or chlorides represented by M (NO ₃ ) _n , M (CO ₃ ) _{n / 2} , M (SO ₄ ) _{n / 2} , and MCl _n (M is an n-valent transition metal). M may be composed of one or more transition metals selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Cd, Zn, Ru, Pd, Ag, Pt, and Au. Examples of the transition metal oxide precursor include nickel nitrate (Ni (NO ₃ ) ₂ ), iron nitrate (Fe (NO ₃ ) ₂ ), and the like. The transition metal included in the transition metal oxide precursor serves to serve as a source for forming the transition metal oxide. The aqueous transition metal oxide precursor solution is preferably a molar concentration of about 0.1 to 5M in order to complex the porous activated carbon powder and the transition metal oxide.

A precipitate is obtained by titrating an alkali compound to an aqueous solution of a transition metal oxide precursor mixed with a porous activated carbon powder. When the alkali compound is titrated so that the pH of the aqueous solution of the transition metal oxide precursor is 8 or more (preferably pH is 8-12), a precipitate is produced. The alkali compound is preferably at least one material selected from lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH) and aqueous ammonia (NH ₄ OH) having strong alkalinity. The alkali compound is preferably a molar concentration of about 0.1 ~ 10M to form a precipitate. The precipitate is in the form of a complex of porous activated carbon and transition metal hydroxide.

The precipitate is selectively separated through filtration and the like, washed with distilled water and dried. The drying is preferably carried out at 60 to 150 ℃ for 10 minutes to 24 hours.

Through the above process it is possible to obtain a material in which the porous activated carbon and the transition metal hydroxide are combined.

A material in which the porous activated carbon and the transition metal hydroxide are combined is charged into a heat treatment apparatus such as an electric furnace and heat treated to form an activated carbon-transition metal oxide composite electrode active material in which the porous activated carbon and the transition metal oxide are combined. The heat treatment may be performed in a furnace, such as an electric furnace, or may be performed using microwaves in a microwave oven. The heat treatment process may be performed in the following manner.

The composite material of porous activated carbon and transition metal hydroxide is charged to a furnace such as an electric furnace and raised to a target heat treatment temperature. In this case, it is preferable that the temperature rise rate of the furnace is about 1 to 50 DEG C / min. If the temperature rise rate of the furnace is too slow, it takes a long time to decrease the productivity. If the temperature rise rate of the furnace is too fast, it is preferable to increase the temperature of the furnace at the heating rate within the above range. At this time, it is preferable that the pressure in the furnace is maintained at normal pressure.

When the temperature of the furnace rises to the target heat treatment temperature, a constant time (for example, 1 to 48 hours) is maintained. The heat treatment is preferably performed in an oxidizing atmosphere such as air or oxygen (O ₂ ). When a certain time is maintained at the heat treatment temperature, the transition metal hydroxide is oxidized to be converted into a transition metal oxide, thereby obtaining an activated carbon-transition metal oxide composite electrode active material in which a porous activated carbon and a transition metal oxide are combined.

Preferably, the heat treatment temperature is about 200 to 600 ° C. If the heat treatment temperature is too high, carbon may be oxidized and energy consumption may be uneconomical. If the heat treatment temperature is too low, the transition metal hydroxide may be converted into a transition metal oxide. Since it may not be converted, it is preferable to heat-treat at the heat-treatment temperature of the said range.

After the heat treatment process, the furnace temperature is lowered to unload the activated carbon-transition metal oxide composite electrode active material in which the porous activated carbon and the transition metal oxide are combined. The furnace cooling may be allowed to cool down in a natural state by turning off the furnace power source, or to set a temperature drop rate (eg, 10 ° C./min) arbitrarily. The pressure inside the furnace is preferably kept constant while the furnace temperature is lowered.

As described above, the heat treatment may be performed using a furnace, such as an electric furnace, but may be performed using a microwave in a microwave oven. In the case of using a microwave, the heat treatment is preferably performed in an oxidizing atmosphere at a temperature of 100 to 200 ° C. Do. In addition, a hydrothermal synthesis method may be used in which a substance obtained by combining porous activated carbon and a transition metal hydroxide is added to distillation, placed in an autoclave, closed with a lid, and then reacted at a temperature of about 100 to 200 ° C. for 1 to 48 hours.

The activated carbon-transition metal oxide composite electrode active material prepared as described above has a plurality of pores that have a mean interlayer distance d ₀₀₂ of 3.602 to 4.445 kPa, a specific surface area of 300 to 1300 m 2 / g, and provide a passage through which electrolyte ions are introduced or discharged. The transition metal oxide is complexed with a porous activated carbon having a. The transition metal oxide is M (O) _{n / 2} , where M is an n-valent transition metal Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Cd, Zn, Ru, Pd, Ag, Pt and One or more transition metals selected from Au).

In order to prepare a porous activated carbon powder having a plurality of pores having an average interlayer distance d ₀₀₂ of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged, the porous activated carbon powder to facilitate complexation with a transition metal oxide Is oxidized in an acidic solution.

The oxidation treatment is intended to facilitate complexation with the transition metal oxide by improving the porous activated carbon powder. The acidic solution is preferably made of at least one acid solution selected from hydrochloric acid (HCl), nitric acid (HNO ₃ ) and sulfuric acid (H ₂ SO ₄ ). In addition, the acidic solution is preferably a molar concentration of about 0.1 to 5M for sufficient oxidation treatment.

The oxidized porous activated carbon is selectively separated, washed and dried. The washing is preferably carried out using distilled water until the pH is neutral. The drying is preferably performed for 10 minutes to 48 hours at a temperature of 100 ~ 200 ℃.

The dried porous activated carbon is dispersed in distilled water. The dispersion is preferably made to be uniform dispersion using the ultrasonic treatment.

An aqueous solution of a precursor metal oxide precursor serving as a source of transition metal is added to the dispersion containing porous activated carbon and mixed.

Transition metal oxide precursors are nitrates, carbonates, sulfates or chlorides represented by M (NO ₃ ) _n , M (CO ₃ ) _{n / 2} , M (SO ₄ ) _{n / 2} , and MCl _n (M is an n-valent transition metal). M may be composed of one or more transition metals selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Cd, Zn, Ru, Pd, Ag, Pt, and Au. Examples of the transition metal oxide precursor include nickel nitrate (Ni (NO ₃ ) ₂ ), iron nitrate (Fe (NO ₃ ) ₂ ), and the like. The transition metal included in the transition metal oxide precursor serves to serve as a source for forming the transition metal oxide. The aqueous transition metal oxide precursor solution is preferably a molar concentration of about 0.1 to 5M in order to complex the porous activated carbon powder and the transition metal oxide.

The alkali compound is titrated into a solution containing the dispersion containing the porous activated carbon and the aqueous solution of the transition metal oxide precursor. The alkali compound is titrated to have a pH of 8 or more (preferably 8 to 12). The alkali compound is preferably at least one material selected from lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH) and aqueous ammonia (NH ₄ OH) having strong alkalinity. The alkali compound preferably has a molar concentration of about 0.1 to about 10 M.

The mixed solution formed by titrating an alkali compound is charged to a microwave oven and heat treated using a microwave. Heat treatment using the microwave is preferably carried out in an oxidizing atmosphere at a temperature of 100 ~ 200 ℃. The microwave oven may be, for example, a device for driving at 1 to 20 GHz, 10 to 300 W to oscillate microwaves. Heat treatment using the microwave is preferably performed for 1 minute to 6 hours.

The reaction product formed by heat treatment using microwaves is washed and dried to obtain an activated carbon-transition metal oxide composite electrode active material.

The activated carbon-transition metal oxide composite electrode active material thus prepared may be used as a supercapacitor electrode. Hereinafter, a method of manufacturing a supercapacitor electrode using an activated carbon-transition metal oxide composite electrode active material will be described.

An activated carbon-transition metal oxide composite electrode active material, a conductive material, a binder, and a dispersion medium are mixed to prepare a composition for a supercapacitor electrode.

The supercapacitor electrode composition may include 2 to 20 parts by weight of a conductive material and 100 parts by weight of the activated carbon-transition metal oxide composite electrode active material based on 100 parts by weight of the activated carbon-transition metal oxide composite electrode active material and the active carbon-transition metal oxide composite electrode active material. 2 to 20 parts by weight of the binder, and 100 to 300 parts by weight of the dispersion medium based on 100 parts by weight of the activated carbon-transition metal oxide composite electrode active material. The composition for the supercapacitor electrode may be difficult to uniformly mix (completely disperse) because it is a dough phase. It may be stirred for a predetermined time (for example, 10 minutes to 12 hours) using a mixer such as a planetary mixer A composition for a supercapacitor electrode suitable for electrode production can be obtained. A mixer such as a planetary mixer enables the preparation of compositions for uniformly mixed supercapacitor electrodes.

The binder is polytetrafluoroethylene (PTFE), polyvinylidenefloride (PVDF), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), polyvinyl butyral (poly vinyl butyral (PVB), poly-N-vinylpyrrolidone (PVP), styrene butadiene rubber (SBR), polyamide-imide, polyimide, and the like. One or more selected species can be mixed and used.

The conductive material is not particularly limited as long as it is an electronic conductive material that does not cause chemical change, and examples thereof include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, super-P black, carbon fiber, copper, and nickel. Metal powders such as aluminum, silver, or metal fibers.

The dispersion medium may be an organic solvent such as ethanol (EtOH), acetone, isopropyl alcohol, N-methylpyrrolidone (NMP), propylene glycol (PG) or water.

Activated carbon-transition metal oxide composite electrode mixture of the active material, the binder, the conductive material and the dispersion medium, the supercapacitor electrode composition is pressed to form an electrode, or the supercapacitor electrode composition is coated on a metal foil to form an electrode, The supercapacitor electrode composition is pushed with a roller to form a sheet and attached to a metal foil to form an electrode, and the resultant formed in an electrode form is dried at a temperature of 100 ° C. to 350 ° C. to form an electrode.

If the example of forming an electrode is demonstrated more concretely, the composition for supercapacitor electrodes can be crimped | molded using a roll press molding machine. The roll press molding machine aims at improving the electrode density through rolling and controlling the thickness of the electrode. The roll press molding machine includes a controller capable of controlling the thickness and the heating temperature of the rolls and rolls at the upper and lower ends, the winding &Lt; / RTI > As the electrode in the roll state passes the roll press, the rolling process is carried out and the roll is rolled again to complete the electrode. At this time, it is preferable that the pressurization pressure of a press is 5-20 ton / cm <2>, and the temperature of a roll shall be 0-150 degreeC. The composition for the supercapacitor electrode, which has undergone the above press pressing process, is subjected to a drying process. The drying process is carried out at a temperature of 100 ° C to 350 ° C, preferably 150 ° C to 300 ° C. If the drying temperature is less than 100 ° C, evaporation of the dispersion medium is difficult and it is not preferable because oxidation of the conductive material may occur during drying at a high temperature exceeding 350 ° C. Therefore, it is preferable that drying temperature is 100 degreeC or more and does not exceed 350 degreeC. And the drying process is preferably carried out for about 10 minutes to 6 hours at the above temperature. Such a drying process is to dry (dispersion medium evaporation) the molded composition for the supercapacitor electrode and to bind the powder particles to improve the strength of the supercapacitor electrode.

In another example of forming the electrode, the composition for the supercapacitor electrode is coated on a metal foil such as a Ti foil, an Al foil, or an Al etching foil Alternatively, the composition for the supercapacitor electrode may be formed into a sheet state (rubber type) by pushing it with a roller and attached to a metal foil to form an anode and a cathode. The aluminum etching foil means that the aluminum foil is etched in an uneven shape. The anode and cathode shapes as described above are subjected to a drying process. The drying process is carried out at a temperature of 100 ° C to 350 ° C, preferably 150 ° C to 300 ° C. If the drying temperature is less than 100 ° C, evaporation of the dispersion medium is difficult and it is not preferable because oxidation of the conductive material may occur during drying at a high temperature exceeding 350 ° C. Therefore, it is preferable that drying temperature is 100 degreeC or more and does not exceed 350 degreeC. And the drying process is preferably carried out for about 10 minutes to 6 hours at the above temperature. Such a drying process allows the composition for the supercapacitor electrode to be dried (dispersed medium evaporates) and simultaneously binds the powder particles to improve the strength of the supercapacitor electrode.

The supercapacitor electrode manufactured as described above may be usefully applied to a small coin-type supercapacitor as shown in FIG. 1 as a high capacity and a wound supercapacitor as shown in FIGS. 2 to 5.

Hereinafter, a method of manufacturing a coin-type supercapacitor will be described with reference to FIG. 1.

FIG. 1 is a sectional view of a coin-type supercapacitor to which the supercapacitor electrode 10 is applied, according to a state of use of the supercapacitor electrode according to the present invention. In FIG. 1, reference numeral 50 denotes a metal cap as a conductor, reference numeral 60 denotes a separator made of a porous material for preventing insulation and short-circuit between the supercapacitor electrodes 10, and reference numeral 70 denotes a leakage preventing electrolyte solution. Gasket for insulation and short circuit prevention. At this time, the supercapacitor electrode 10 is firmly fixed to the metal cap 50 by an adhesive.

The coin type supercapacitor includes a positive electrode made of the above-described supercapacitor electrode, a negative electrode made of the above-described supercapacitor electrode, a separator disposed between the positive electrode and the negative electrode, Is placed in a metal cap, and an electrolyte solution in which an electrolyte is dissolved is injected between the anode and the cathode, followed by sealing with a gasket.

The separator may be a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyester nonwoven fabric, a polyacrylonitrile porous separator, a poly (vinylidene fluoride) hexafluoropropane copolymer porous separator, a cellulose porous separator, a kraft paper or a rayon fiber, and the like. If the separator is generally used in the field is not particularly limited.

On the other hand, the electrolyte solution filled in the supercapacitor of the present invention is an aqueous solution in the form of an aqueous solution, the electrolyte is a water-soluble electrolyte consisting of sulfuric acid, 10 to 60% by weight of the electrolyte, 40 to 90% by weight of water, or lithium hydroxide, potassium hydroxide And at least one alkali-based electrolyte selected from the group consisting of sodium hydroxide and a water-soluble electrolyte having a concentration of 0.5 to 3 M.

Hereinafter, a method of manufacturing a wound supercapacitor will be described with reference to FIGS. 2 to 5. 2 to 5 are views showing a wound supercapacitor.

As shown in FIG. 2, the lead wires 130 and 140 are attached to the anode 120 and the cathode 110 prepared by coating the composition for the supercapacitor electrode on a metal foil or making a sheet state and pasting the metal foil.

As shown in FIG. 3, the first separator 150, the anode 120, the second separator 160, and the working electrode 110 are stacked, coiled, and wound in a roll form. After fabrication at 175, the roll shape is wound around the roll with adhesive tape 170 or the like.

The second separator 160 between the anode 120 and the cathode 110 prevents shorting between the anode 120 and the cathode 110. The first and second separators 150 and 160 are polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, polyacrylonitrile porous separator, poly (vinylidene fluoride) hexafluoropropane copolymer porous separator, cellulose porous separator, kraft paper Or if the separator is generally used in the field of batteries and capacitors, such as rayon fibers are not particularly limited.

As shown in Fig. 4, a sealing rubber 180 is mounted on a roll-shaped product and is mounted on a metal cap 190 (e.g., an aluminum case).

The electrolyte is injected and sealed so that the roll-shaped winding element 175 and the lithium foil 195 are impregnated. The electrolytic solution is an aqueous solution in the form of an aqueous solution, the electrolyte being a water-soluble electrolyte containing 10 to 60% by weight of electrolyte and 40 to 90% by weight of water, or at least one selected from the group consisting of lithium hydroxide, potassium hydroxide and sodium hydroxide. It may be a water-soluble electrolytic solution composed of at least one alkaline electrolyte and having a concentration of 0.5 to 3 M.

Hereinafter, experimental examples according to the present invention will be presented, and the present invention is not limited to the following experimental examples.

Anshan Pitch (Anshan Chemical, China), a graphitizing carbon material, was carbonized in a nitrogen atmosphere. The carbonization treatment was performed for 2 hours at a temperature of 600 ℃.

The carbonized carbon material and potassium hydroxide (KOH) were mixed at a weight ratio of 1: 4 and ground using a dry ball milling process. The ball milling process using a zirconia ball, the size of the ball was about 5mm, the rotation speed of the ball mill was set to about 100rpm, ball milling was performed for 2 hours. An activation sample mixed with carbon material and potassium hydroxide was charged to a nickel (Ni) reactor, and an activation treatment was performed at 900 ° C. for 2 hours in an argon (Ar) atmosphere.

The activated sample was neutralized with 0.1 M hydrochloric acid (HCl), thoroughly washed five times with distilled water, and dried at a temperature of 150 ° C. for 24 hours to obtain a porous activated carbon powder.

The porous activated carbon powder thus prepared has an average interlayer distance d ₀₀₂ of 3.602 to 4.445 kPa, a specific surface area of 300 to 1300 m 2 / g, and a large number of pores that provide passages through which electrolyte ions and dispersion mediums are introduced or discharged. Made of porous carbon.

0.2 g of the porous activated carbon powder prepared as described above was oxidized in a 30 ml acid solution. As the acidic solution, 1M nitric acid (HNO ₃ ) solution was used.

The acidic solution containing the oxidized porous activated carbon was added to 3 ml of a 1.0 M nickel nitrate (Ni (NO ₃ ) ₂ ) solution, which is an aqueous transition metal oxide precursor solution, and mixed.

An alkali compound 1.0M lithium hydroxide (LiOH) was titrated into a nickel nitrate solution mixed with porous activated carbon powder to obtain a precipitate. The lithium hydroxide (LiOH) was titrated to pH 9 of the nickel nitrate solution.

The precipitate was washed five times with distilled water, selectively separated through filtration and dried. The drying was carried out at 80 ° C. for 24 hours.

Through such a process, porous activated carbon and nickel hydroxide (Ni (OH) ₂ ) are complexed.

The porous activated carbon and nickel hydroxide (Ni (OH) ₂ ) composite material was charged into a heat treatment apparatus, heated to 2 ° C./min, heat treated at 300 ° C. for 12 hours, and cooled to cool the porous activated carbon and nickel oxide (NiO). The activated activated carbon-transition metal oxide composite electrode active material was obtained.

The activated carbon-transition metal oxide composite electrode active material has a porous activated carbon having an average interlayer distance d ₀₀₂ of 3.602 to 4.445 kPa, a specific surface area of 300 to 1300 m 2 / g, and a plurality of pores that provide passages through which electrolyte ions are introduced or discharged. Nickel oxide (NiO) is a compound.

6 is a high resolution-transmission electron microscope (HR-TEM) photograph of an activated carbon-transition metal oxide composite electrode active material prepared according to Experimental Example 1. FIG.

Referring to FIG. 6, it can be seen that nickel oxide (NiO) is combined with porous activated carbon.

7 is a graph showing an X-ray diffraction (XRD) pattern of the activated carbon-transition metal oxide composite electrode active material prepared according to Experimental Example 1. FIG.

Referring to FIG. 7, it was confirmed that the activated carbon-transition metal oxide composite electrode active material prepared according to Experimental Example 1 had a carbon (C) and a NiO crystal phase.

Activated carbon-transition metal oxide composite electrode active material prepared as described above, Super-P black ((Belgium, MMM), a conductive material, carboxymethyl cellulose (CMC), a binder, styrene butadiene rubber (SBR) ) Was mixed in a weight ratio of 85: 5: 5: 5 and distilled water as a dispersion medium was prepared to prepare a composition for a supercapacitor electrode, which was a planetary mixer (manufacturer: TK, model name: Hivis disper). Was mixed by stirring for 1 hour using a planetary mixer.

The supercapacitor electrode composition thus prepared was coated on a titanium foil (Ti foil) with an area of 1 cm × 1 cm and dried to prepare a supercapacitor electrode. The drying was carried out for 2 hours at a temperature of 120 ℃.

In order to observe the characteristics of the supercapacitor electrode manufactured according to Experimental Example 1, the following experiment was conducted.

As shown in FIG. 8, platinum (Pt) is used as a counter electrode (210), a supercapacitor electrode manufactured according to Experimental Example 1 is a working electrode (220), and a saturated calomel electrode (SCE). The three-electrode cell was configured using the reference electrode 230. The three-electrode cell was implemented in a beaker 240 having a capacity of 250 ml, and 6 M potassium hydroxide (KOH) solution was used as the electrolyte. 9 is a plan view of the three-electrode cell viewed from above. FIG. 10 is a cycle measuring the current value of an electrode when the electrode potential of the three-electrode cell shown in FIGS. 8 and 9 is changed while maintaining a constant scan rate at a constant potential scanning rate within a potential window. It is a cyclic voltammogram graph.

Referring to FIG. 10, the pseudocapacitor behavior was observed at 0.0 to 0.9V while maintaining the potential scanning speed of 5mVs ^- ^1, which showed a very reversible reaction and a specific electrolytic capacity of 277.8Fg ^-1 .

Activated carbon-transition metal oxide composite electrode active material prepared according to Experimental Example 1, Super-P black (Belgium, MMM), a conductive material, carboxymethyl cellulose (CMC), a binder, styrene butadiene rubber (SBR) ) Was mixed in a weight ratio of 85: 5: 5: 5, and distilled water as a dispersion medium was mixed thereto to prepare a composition for a supercapacitor electrode. The mixing was performed using a planetary mixer (manufacturer: T.K, model name: Hivis disper), and mixed by stirring for 1 hour using a planetary mixer.

The supercapacitor electrode composition thus prepared was coated on an aluminum etching foil and subjected to a drying process. The drying process was performed for 2 hours in a convection oven of about 120 ℃.

The dried resultant was punched to φ12 mm to prepare a supercapacitor electrode specimen having a size of 12 mm in diameter and 1.2 mm in height.

A supercapacitor-type supercapacitor having a diameter of 20 mm and a height of 3.2 mm was prepared using the prepared supercapacitor electrode specimens as the anode and the cathode. In this case, in preparing a coin cell, TEABF ₄ (tetraethylammonium tetrafluoborate) 1M was added to a propylene carbonate (propylene) solvent, and TF4035 (manufactured by NKK, Japan) was used as a separator.

Figure 11 shows the results of the charge (charge) and discharge (discharge) test of the supercapacitor thus manufactured.

Referring to FIG. 11, as a graph for charging and discharging up to 0.1 to 1.0V, a charge and discharge test with a current of 1 mA per electrode active material area showed a specific storage capacity of 303.5 F / g.

0.2 g of the porous activated carbon powder prepared as described above was oxidized in 100 ml of acidic solution. As the acidic solution, 1M nitric acid (HNO ₃ ) solution was used.

The oxidized porous activated carbon was selectively separated through filtration, washed with distilled water until pH reached 7, and dried. The drying was carried out at 150 ° C. for 24 hours.

0.2 g of the oxidized and dried porous activated carbon was added to 100 g of distilled water, and the mixture was sonicated and uniformly dispersed.

0.34 ml of a 1.0 M nickel nitrate (Ni (NO ₃ ) ₂ ) solution, which is an aqueous transition metal oxide precursor solution, was added to the dispersion containing the oxidized porous activated carbon and mixed with stirring. The stirring was carried out at about 100rpm.

An alkali compound 1.0 M lithium hydroxide (LiOH) was titrated into a nickel nitrate solution mixed with porous activated carbon powder. The lithium hydroxide (LiOH) was titrated to pH 9 of the nickel nitrate solution.

The mixed solution formed by titrating lithium hydroxide (LiOH) was reacted for 10 minutes at 2.45 GHz, 100 W in a microwave oven at 120 ℃ temperature conditions.

The reaction product produced using the microwave was washed five times with distilled water, selectively separated by filtration and dried. The drying was carried out at 80 ° C. for 24 hours.

Through the above process, an activated carbon-transition metal oxide composite electrode active material in which porous activated carbon and nickel hydroxide (Ni ₂ ) were combined was obtained. The activated carbon-transition metal oxide composite electrode active material has a porous activated carbon having an average interlayer distance d ₀₀₂ of 3.602 to 4.445 kPa, a specific surface area of 300 to 1300 m 2 / g, and a plurality of pores that provide passages through which electrolyte ions are introduced or discharged. Nickel oxide (NiO) is a compound.

In order to observe such characteristics as the average interlayer distance of the porous activated carbon powder, the following experiment was conducted.

Anshan pitch (Anshan Chemical, China), which is a graphitizing carbon material, was carbonized in a nitrogen atmosphere according to the temperature conditions (carbonization temperature) shown in Table 1. The carbonization treatment was performed for 2 hours at temperatures of 550 ° C, 600 ° C, 650 ° C, 700 ° C, 750 ° C, 800 ° C, 850 ° C and 900 ° C, respectively.

The carbonized carbon material and potassium hydroxide (KOH) were mixed at a weight ratio of 1: 4 and ground using a dry ball milling process. The ball milling process using a zirconia ball, the size of the ball was about 5mm, the rotation speed of the ball mill was set to about 100rpm, ball milling was performed for 2 hours. An activation sample mixed with carbon material and potassium hydroxide was charged to a nickel (Ni) reactor, and an activation treatment was performed at 800 ° C. for 2 hours in an argon (Ar) atmosphere.

The activated sample was neutralized with hydrochloric acid (HCl) and washed with distilled water to obtain a porous activated carbon powder as an electrode active material for a supercapacitor.

The porous activated carbon prepared in this way has an average interlayer distance d ₀₀₂ of 3.602 to 4.445 kPa, a specific surface area of 300 to 1300 m 2 / g, and a porous having a large number of pores that provide passages through which electrolyte ions and dispersion mediums are introduced or discharged. Made of carbon.

The porous activated carbon prepared as described above, Super-P black (Belgium, MMM), a conductive material, carboxymethyl cellulose (CMC) as a binder, and styrene butadiene rubber (SBR) as a binder are 85: 5: 5: The mixture for 5 weight ratio and distilled water which is a dispersion medium was mixed here, and the composition for supercapacitor electrodes was produced. The mixing was performed using a planetary mixer (manufacturer: T.K, model name: Hivis disper), and mixed by stirring for 1 hour using a planetary mixer.

The supercapacitor manufactured according to Experimental Example 3 was subjected to aging by applying a voltage of 2.7V at 70 ° C., and the capacity was measured by charging and discharging up to 2.7V. The specific capacitance was calculated by dividing the measured capacity by the volume of the positive and negative electrodes. The average interlayer distance d ₀₀₂ value and the non-power storage capacity of the carbonization conditions was shown in the Table 1 below.

Carbonization temperature (℃) Reserve capacity (F / cc) d ₀₀₂ (Å) 550 21.1 4.445 600 22.4 4.443 650 27.7 4.340 700 33.3 4.220 750 31.8 3.952 800 28.4 3.888 850 24.7 3.798 900 22.4 3.602

As can be seen in Table 1 above, the highest specific storage capacity was obtained at a carbonization temperature of 700 to 750 ° C., and the average distance d ₀₀₂ between the layers was 3.952 to 4.220 Å.

FIG. 12 is an electrochemical activation graph of a supercapacitor manufactured according to Experimental Example 3, showing charge and discharge test results for 2.7V.

FIG. 13 is a graph showing specific capacitance according to carbonization temperature of a supercapacitor manufactured according to Experimental Example 3. FIG. Referring to FIG. 13, the highest specific capacitance was shown at a carbonization temperature of 700 to 750 ° C.

14 is a graph showing the average interlayer distance according to the carbonization temperature of the supercapacitor manufactured according to Experimental Example 3. Referring to FIG. 14, the average interlayer distance d ₀₀₂ of the porous activated carbon at the carbonization temperature of 550 ° C. was about 4.445 kPa. As the carbonization temperature was increased, the average interlayer distance d ₀₀₂ of the porous activated carbon decreased gradually, and 900. The average interlayer distance d ₀₀₂ of the porous activated carbon at a carbonization temperature of ℃ was about 3.602 kPa.

15 is a high resolution-transmission electron microscope (HR-TEM) photograph showing a carbon material before carbonization treatment after carbonization according to Experimental Example 3, and FIG. 16 is a high resolution-transmission electron showing porous activated carbon prepared according to Experimental Example 3 It is a microscope (HR-TEM) photograph. Referring to FIGS. 15 and 16, the carbonized carbon material may be seen to have a plurality of layers spaced apart by an interlayer distance, and the porous activated carbon may have a plurality of pores.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.

10: super capacitor electrode 50: metal cap
60: Membrane 70: Gasket
110: working electrode 120: positive electrode
130: first lead wire 140: second lead wire
150: first separator 160: second separator
170: Adhesive tape 175: Winding element
180: sealing rubber 190: metal cap
195: lithium foil
210: counter electrode 220: working electrode
230: reference electrode 240: beaker

Claims

It is a nanocomposite material in which a transition metal oxide is composited into porous activated carbon having a plurality of pores which have an average interlayer distance d ₀₀₂ of 3.602 to 4.445 Å and provide a passage through which electrolyte ions are introduced or discharged. ,
The transition metal oxide is M (O) _{n / 2} , where M is an n-valent transition metal, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Cd, Zn, Ru, Pd, Ag, Pt Activated carbon-transition metal oxide composite electrode active material, characterized in that the material having a chemical formula of one or more transition metals selected from Au.

The activated carbon-transition metal oxide composite electrode active material according to claim 1, wherein the specific surface area of the porous activated carbon is in the range of 300 to 1300 m 2 / g.

Preparing a porous activated carbon powder having a plurality of pores having an average interlayer distance d ₀₀₂ in a range of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged;
Oxidizing the porous activated carbon powder in an acidic solution to facilitate complexation with a transition metal oxide;
Adding and mixing the acidic solution containing the oxidized porous activated carbon powder to an aqueous solution of a transition metal oxide precursor serving as a source of the transition metal;
Obtaining an precipitate by titrating an alkali compound to the aqueous transition metal oxide precursor solution in which the porous activated carbon powder is mixed;
Selectively separating the precipitate to obtain a material having a transition metal hydroxide complexed with porous activated carbon; And
A method of manufacturing an activated carbon-transition metal oxide composite electrode active material comprising the step of heat-treating a material in which a transition metal hydroxide is complexed to porous activated carbon in an oxidizing atmosphere to obtain a nanocomposite material in which a transition metal oxide is complex to porous activated carbon.

Preparing a porous activated carbon powder having a plurality of pores having an average interlayer distance d ₀₀₂ in a range of 3.602 to 4.445 kPa and providing a passage through which electrolyte ions are introduced or discharged;
Oxidizing the porous activated carbon powder in an acidic solution to facilitate complexation with a transition metal oxide;
Selectively separating the oxidized porous activated carbon, followed by washing and drying;
Dispersing the dried porous activated carbon in distilled water;
Adding and mixing an aqueous transition metal oxide precursor solution serving as a source of transition metal to a dispersion containing porous activated carbon;
Titrating an alkali compound in a solution containing the dispersion containing the porous activated carbon and an aqueous solution of a transition metal oxide precursor;
Charging a mixed solution formed by titrating an alkali compound into a microwave oven and heat-treating using microwaves; And
Method of manufacturing an activated carbon-transition metal oxide composite electrode active material comprising the step of washing and drying the reaction product formed by heat treatment to obtain a nanocomposite material in which a transition metal oxide is complexed with porous activated carbon.

The method of claim 3, wherein the heat treatment is performed in an oxidizing atmosphere at a temperature of 200 to 600 ° C. 5.

5. The method of claim 4, wherein the heat treatment using the microwave is performed in an oxidizing atmosphere at a temperature of 100 to 200 ° C. 6.

The acidic solution of claim 3 or 4, wherein the acidic solution comprises at least one acid solution selected from hydrochloric acid (HCl), nitric acid (HNO ₃ ), and sulfuric acid (H ₂ SO ₄ ). A method for producing an activated carbon-transition metal oxide composite electrode active material, characterized in that the molar concentration is in the range of 0.1 to 5M.

The transition metal oxide precursor of claim 3 or 4, wherein M (NO ₃ ) _n , M (CO ₃ ) _{n / 2} , M (SO ₄ ) _{n / 2} , MCl _n (M is an n-valent transition metal). Nitrate, carbonate, sulfate or chloride represented by Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Cd, Zn, Ru, Pd, Ag, Pt and Au). Made up of
The transition metal oxide precursor aqueous solution is a method for producing an activated carbon-transition metal oxide composite electrode active material, characterized in that the molar concentration ranges from 0.1 to 5M.

According to claim 3 or 4, wherein the alkali compound is at least one material selected from lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH) and ammonia water (NH ₄ OH), the alkali compound is A method for producing an activated carbon-transition metal oxide composite electrode active material, characterized in that the molar concentration is in the range of 0.1 to 10M.

The method for producing an activated carbon-transition metal oxide composite electrode active material according to claim 3 or 4, wherein the alkali compound is titrated to have a pH of 8 to 12.

According to claim 3 or 4, wherein preparing the porous activated carbon powder,
Carbonizing the carbon material in an inert atmosphere at a temperature in the range of 550-1000 ° C .;
Activating the carbonized carbon material by mixing with alkali; And
A method for producing an activated carbon-transition metal oxide composite electrode active material comprising neutralizing and rinsing an activated product with an acid.

The method of claim 11, wherein the activating process comprises:
Mixing the carbonized carbon material with the alkali in a weight ratio of 1: 1 to 1: 5;
Pulverizing the mixed result; And
Heat treatment in an inert atmosphere at a temperature of 600-900 ° C.,
The alkali is a method of producing an activated carbon-transition metal oxide composite electrode active material, characterized in that potassium hydroxide (KOH) or potassium hydroxide (NaOH).

The method according to claim 3 or 4, wherein the specific surface area of the porous activated carbon powder is in the range of 300 to 1300 m 2 / g.